Appabattts fob producing diolemns



G. MER'SEI-ZEAU. APPARATUS FOR PRODUCING DIOLEFINS. APPLICATION FILED SEPT. 14. I912. RENEWED 05c. I3. 1918.

Patented July 8, 1919.

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UNITED sTArnsPATENT onmon.

our. irnnsnnnau, or NEW comm,

YORK, N.'Y.,- ASSIGNOB TO CHEMICAL DEVELOPMENT A CORPORATION" OF MAINE.

APPARATUS FOR PRODUCING DIOLEFINS.

Specification of Letters Patent.

Patented July 8, 1919.

Application filed September 14, 1912, Serial No. 720.363. Renewed December 13, 1918. Serial No. 266.651.

To all whom it may concern:

'Be it known that I Gan. Mnnsnnnau, a citizen'of the United, States, residing at State of New York, have invented certain new and useful Improvements in Apparatus for Producing Diolefins, of which the following is a specification.

This invention relates apparatus for producing diolefins; and it comprises a method wherein a gas rich in olefins and containing diolefins is treated to remove such diolefins and thereafter heated to produce a further quantity of diolefins, such removal of diolefins and heating to produce more being re eated as many times it also comprises an organization of apparatus elements comprising consecutively arranged means for roducing a. gas rich in olefins and diole s, means to processes of and for removing diolefins therefrom, means for heating the treated gas to produce more diolefins and newly produced diolefins; all as more fully hereinafter set forth and as claimed.

In another and copending application, Serial No. 713,585, filed Aug. 6, 1912, is described and claimed a method of producing gas rich in olefins wherein heavy oil vapors are exposed for a limited time as by passing through a relatively short an narrow tu e,

to a regulated heating at a temperature around 700 C. under conditions not producing a total gasification of such oil; that is, permitting a, substantial amount of heavy oil vapors to pass through with the gas duced. The oil vapors are condensed out of the as and returned in admixture with fresh 0%1 to the heating zone. It has been found that by passing heavy oil vapors throu h a comparatively short and narrow heate tube in this manner a duced carrying 45 to 50 per cent. total ole ns, t or 5 per cent. acetylenic gases, 4 to 5 per cent. diolefins with aresidue consisting mainly of saturated gases, such as ethane. The best results were attained with iron or steel tubing ranging inch internal diameter heated within 20 or 30 degrees on either side of 700 C. At 650 C. the action is slow and at 750 perhaps too rapid, while about 800 C. 1s a danger line which should not be exceeded. Absence of coky carbon is necessary for smooth thermolysis, since it exercises an unof New York andmeans for recovering the.

pro-

gas can be robetween 0.25 and 1.5

desirable atalytic action upon the gas, producing more carbon and causing the tubes to plug up. Softer forms of carbon, such as soot and lampblack, do not have this action, to such an extent. With proper regulation of conditions, the oil is gasified out formation of tar or carbon.

In this prior work it was found that while rich olefin'c gas could be made under the stated conditions within rather wide limits in the length of the heated zone, that is, with great variations in the time-heat factor, yet there were im ortant variations in the mutual ratios of t e various unsaturated gases to each other. A good conversion to form olfinic gases with no more than 6 inches of travel through a heated zone while 90 inches and more of travel are not injurious under proper heating and other conditions. With a shorter length of travel, up to say 30 to 45 inches, the proportion of diolefins is about 4 to 5 per cent. of the total gas and the ethylene is present in much larger amount than propylene and the butylenes. With a. longer travel of the oil vapors through a heated zone, up to say 90 inches, the proportion of propylene relative to ethylene rises and the percentage of withcan be attained diolefins also increases up to about 8 percent.

I have now about 8 per cent. limit; a limitin found that this proportion of represents a maximum partial pressure, that the formation of diolefins goes on till about this percentage is reached, the exact percentage varying somewhat wit 1 temperature and other conditions) and then ceases. This formation of diolefins appears to be at the expense of the olefins proper. If the heating be interrupted when this maximum is reached, the as cooled to remove oil vapors and the diolefins removed and recovered, upon reheating the gas to about the temperature at which it was originally formed a, fresh crop of diolefins is formed. Here again the maximum limit seems to be about 8 per cent. On removing the newly produced diolefins and once more heatin the residual gas, more are produced, the imit again seeming to be about8 per cent. Repetition of the treatment will give a fourth crop; but this time the amount is generally only about 6 per cent. Subsequent treatments ordinarily are hardly worth while. The residual gas after the described pronot necessary mercially valuable.

duction' and removal of diolefins still has a high heating and lighting value; and some portion ofit may be usefully employed in furnishing the heat necessa operations. A less valuab e gas may of course be used instead for heating purposes. In the reheatin of the gas to produce successive crops oEdiolefins it is not necessary to have oil vapors in the sphere of reaction and their use introduces practical complications in the operation. Except in the original formation of the gas therefore I ordinarily do not heat in the presence of oil vapors. In the reheating, the tempera tures may advantageously be, as in the original production of the as, around 700 C. Coky carbon is better a sent.

hile my process of removing diolefins and heating to produce more diolefins is applicable to any gas rich in olefins and containing diolefins, I regard it as particularly applicable to the gas produced 'asdescribed. Asa gas making material may be used any crude petroleum or analogous hydrocarbonmateriali Gas oil or other still residuums substantially'freed of low-boiling constituents are very advantageous. Petroleums containing cyclic hydrocarbons on gasificationj produce more or less benzol, toluol, xylols, etc., and therefore less amounts of. olefins, and, concomitantly, less per gallon of oil. How- "even-these'aromatic hydrocarbons are readily separable from the diolefins and are com- In the described way of producing the olefinic gas from gas oil with the subsequent production of several crops of diolefins under the present invention, over a quarter of the oil may be converted into diolefins.

Ordinarily in oil vapors, or gas, to '90 inches of rather narrow 0.25 to 0.75 inch internal diameter. terra cotta, tubes may be used they have no special advantage o-ver steel or iron. Catalysts are for successful 0 eration. Coky carbon should be absent an should it form, the operation should be interrupted to removeit. For this reason it is desirable each heating" passage of the I prefer to use about tubing, say While to arrange the heating tubes or tube retorts so that they can be readily cleaned, as by thrusting a cleaning rod through. As many tubes or tube retorts may be employed operating in parallel as may be desired; it being better to gain capacity in this way rather than by increasing the diameter of the tubes.

The diolefins formed in the successive crops may be removed and recovered in any desired way, as by scrubbing with sulfuric acid of appropriate strength and emperature, by combining with SO whi forms compounds readily resolved by heat by compression of the gas, by chilling or y the use in the various freezing contemplated in this invention copper, bronze, aluminum, etc,

1,eos,co2

of a cold wash oilf The cold wash oil is an advantageous means since itreadily yields or releases its. absorbed diolefins in vapor form on Warming. Gas oils or heavy liquid rcsidua; rich in aromatic series components may be advantageously used as awash oil since such oils can be obtained having a good absorptive power for diolefins and apoint sufliciently low to. permitefiicient chilling. The same quantity of wash oil may of course beused over and over again, circulating cyclically through absorbers and: releasers. Where compression of the gas is used in recovering the diolefins, it is advantageous to use a little cold oil also. While the diolefins particularly have boiling points ranging from 0 to 56 0., yet be cause of their relatively high vapo tension and their small proportion in the gas it is diflicultto remove them all by a simple com pression or a some such expedicrrtas a portion of cold oil as an absorbing solvent. 'lihe use of chilled.

oil as a liquid in a device like a scrubber or a co-umn still is quite satisfactory and is relatively simple. The same current of chilled oil. may in a plurality of absorbers.

n the accompanying illustration I have shown, more or less diagrammatically in vertical section, some parts being in elevation, a typical organization of apparatus elements within the prmen-t invention and useful inthe operation of the described process- In this showing,.-

Element 1 is a suitable furnace chamber. In this chamber are, as shown, four banks, A, B, O, and 1),.of tube retorts, the retorts of A serving to transform oilinto. gas core taining olefins and diolefins and those oi B, C, generators.- as many sets of In each bank, there may be tube retorts operating in parallel as ma be desired. The tube rctorts, as shown, in all the banks are similar and consist of a length 3 of narrow tubing from 0.25 to 1 inch internal diameter connected with another length or return tube 4- by vertical connection 5. Each length may have an extension of 4:0 or 50 inches Within the furnace chamber. Caps. 6 and 7 at the ends of each tube enable a cleaningrodto be thrust through.

951- is supplied fromreservoir 8 by means-- of pump 9 to main 10- which may teed any number of tube retorts operating in parallel in bank A. The connection between the malngand each tube retort is valved at 11', permitti any individual tube retort to be cut out or cleaning without interruptingthe operation of the others in the bank. The tube retorts are, as shown, best supplied with liquid oil or given a flooding feed as this is more convenient than the chilling without the use ofbe used for operat-- and-D being reheaters, or diolefin generation of oil vapors elsewhere with nature for heating and lighting, is best used the heavy, high-boiling oils most advanfor such purposes. It may however be tageously used in the resent invention. passed over a catalyst, such as nickel or The gas formed in the tu e retorts of bank palladium, or both together, on a carrier,

A and the excess of oil vapors pass into such as'petroleum coke, at about 200 C. to 70 main 12. Using heavy oils as raw material produce more olefins and then the described this may be simply air-cooled, but it gives heating and absorbing operations repeated. an economy of space to use a surfacecon- The gas passing the fourth absorber denser such as 13 of a well known type. shown is still rich in ethane and other gases Thismay be fedrwith oil through 14, the of high heating and lighting value. It may-75 oil passing through and going to the reserbe sent through conduits 44 and 45 to any voir through pipe 15. The condensate suitable place of use; or it may be treated drains back into the reservoir where-'t mixes as described. A portion may be sent with the fresh oil and is returned or pasthrough 46 to supply heat in the furnace.

15 sage throu h the retorts in admixture with The diolefins in the gas from retorts A so such oil. he condensed oil always contains are not usually as pure as those recovered some cracked products of the nature of from the reheated gas in later operations. gasolene and kerosene, but there is usually The diolefin recovered in scruppers 43 and a larger proportion of unchanged original 36 maybe substantially pure divinyl. In

oil and the volatile cracked products are 19 some aromatic hydrocarbons may be 85 absorbed and held back by this oil; they taken up. The gas-making operation does are scrubbed out. The gas passing the connot form the aromatic hydrocarbons from denser is urged by umps or impellers 17, the aliphatic but if the original oil conwhich may put it under as much pressure as tains such hydrocarbons they may reappear may be desired, past chiller 18 into absorber in the gas. For this reason it .is usually 90 19. The chiller is best given a slight slant .worth while recovering the diolefins from toward 'the absorber to facilitate drainage 19 separately from those recovered later. thereto. The absorber may be any ordinary For this purpose this absorber may be contype of scrubber or it may be constructed nected to a separate still.47 having a heat something like a column still with cups and interchanger 48 acting as a goose. In lien 95 plates to facilitate intimate contact of the however of Sending con n a s k int gas with the cold oil supplied through inlet the still, as is usual with such an inter- 20. The gas freed of its diolefins and changer, they may be removed by outlet 49. quite cold passes through 21 to a heat inter- This will dispose of most of the gasolenes or changer 22 and thence to a gas ma1n 23 benzols which go forward. The uncon- 100 supplying the tube retorts of bank B. In (3811566. P P out through P p 50 the tube retorts of this bank the gas is repump 51 where they are liquefied to form heated and diolefins produced. The hot gas mm i l fi which y be P g goes to main 24 and thence through the heat in drums.

interchanger and .conduit 25 past pump or The still may be run at a temperature of 105 impeller 26 and chiller 27 to absorber 28. about 70 to 80 C. The wash 011 from the I Here it is once more treated with chilled still or releaser (47) passes by pump 52 to 011130 remove diolefins. After scrubbing it and through cooler 53, where it may be goes through conduit 29 and heat inter- C oled by water and thence by conduit 54 changer 30 to main 31 supplying the retorts t0 chiller 55 where its temperature may be 110 of bank C. In this bank it is once more lowered to about -15 C. by circulating heated to-produce more diolefins. It passes brine or calcium chlorid solution. Thence it from bank C to main 32 and thence through passes to and through the series of absorbthe heat interchanger and conduit 33 past ersl A special valved pipe (20) may lead a impeller 34 through chiller 35 to absorber portion to the first absorber in series (19) 115 Here it gives up its new charge of to enable its independent operation. When diolefins to the chilled oil and is then sent this independent operation of the absorber through conduit 37 and heat exchanger 38to operating on the original oil gas is desired,

- main 39 supplying the tube retorts of bank a special still 56, rovided with heat inter- D. From these retorts it passes to main changer or goose 57, of ordinary construc- 120 40, thence through conduit 41 and the heat tion may be used. Vapors from this may interchange! past impeller 42 and chiller be passed'through outlet 57+ to a liquefy- 42 to andthrough absorber 43 to remove ing pump (not shown) to roduce diolefins the diolefins. rich in divinyl. The chilled oil passes from 60 The operation may be repeated, but in one absorber to another, taking up diolefins 12 general after four heating operations the as it goes, the connection between the abamount of olefins diminishes to such an ex- .sorbers being designated 58. A special tent that the production of diolefins becomes valved connection 59 enables the absorber quite small and asa rule at this point the for reheated gas and the absorber (19) for residual gas, which is still of a desirable oil gas to be used together. In this event, 1 0

7 tube,

the still just described (56) is not used.

rine or calcium chlorid may be chilled in refrigerator 60 and sent by pump 61 and conduit 62 through the oil chiller (55) and the successive gas chillers back to the refrigerator.

Some oil-s leave a carbonaceous residue on evaporation, this coming apparently at least in part from naturally contained free carbon; and this carbon should be removed from the oil feed end of the tube retorts of bank A as it accumulates in using such oils This carbon does not have the same prej udicial catalytic effect as the hard coky carbon formed, apparently by the decomposition of methane, by heating gases to high temperatures.

What I claim is 1. The combination with a retort, of heating means therefor adapted to maintain it at a uni orm low heat to convert petroleum into gas, means for recovering unchanged oil vapors from such gas, means for recovering diolefins from the treated gas, means for reheating the gas to produce a further quantity of diolefins and means for recovering such further quantity. 2 In a diolefinmaking plant a narrow means for supplying oil thereto, means for heating the tube, means for cooling gas coming therefrom to recover residual oil, means for recovering diolefins, means for transmitting the gas through another narrow tube and means iior recovering diolefins from the gas "issuing from such other tube. 3. In a diol'efin plant, the combination with a retort comprising a plurality of tubes, of single means for heating all said tubes, means supplying oil to said retort, in excess of the amount permanently volatilized by said heating means, means condensing and removing excess oil from the gas produced, means for removing diolefins from said gas, a second retort also comprising a plurality of tubes, connections leading the treated gas through said second retort, and means beyond said retort for removing diolefins.

treated gas back to ascents 4%. In a diolefin plant, a plurality of tube retorts arranged in series, means for heating such retorts, means for passing oil through the first retort, means connected with and beyond the retort for condensing out oily bodies from the gas produced, means for recovering diolefins from such gas, means for returning the gas through the succeeding retorts and means beyond each such succeeding retort for recovering diolefins from the emerging gas. v I

5. In a diolefin plant, a furnace chamber, a series of tube retorts therein, means for supplying oil to one such condensing and removing oil from thegas produced therein, means for removin diolefins from such gas, connections leadmgthe another suchretort and. means connected with and' beyond: such retort for removing diolefins.

6. In a diolefin torts arranged: in series, connections includ ing a scrubbing device lior passing gas from one retort to the next, and means for supplyin chilled oil to such scrubbing device.

7. li n a diolefin plant, a plurality of retorts arranged in series, connections including a scrubbing device between successive retorts, and means for supplying chilled oil to such scrubbing device.

, 8. In a diolefin plant, a furnace chamber, a series of tube retorts therein, means tor supplying oil to one such retort, means for condensing and removing oil from the gas produced therein, means for remoying diolefins from the gas produced therein, means for dissolving out diolefins from such gas, connections leading another such retort, means beyond such retort for dissolving out diolefins, and means for recovering diolefins from the solution which they are contained.

, In testimony whereof, I afix my signature 'n the presence oat two subscribing witnesses.

GAIL MERSEREAU. Witnesses:

A. L. VINonN'r, PAUL R. Han.

retort, means for plant, a plurality of re 

